Cracking a naphtha with a cracking conversion catalyst comprising a synthetic mordenite zeolite



zeolites.

United States Patent 3,247,098 CRACKING A NAPHTHA WITH A CRACKEN CONVERSION CATALYST COMPRISKNG A SYN- THETIC MORDENHTE ZEOLKTE Charles Newton Kimberiin, JL, Baton Rouge, La, as-

signor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Nov. 12, 1963, Ser. No. 323,130 11 Claims. (Cl. 208-120) The present invention deals with improved means of obtaining high octane gasolines b-y cracking hydrocarbons with certain synthetic crystalline alumina-silicate More particularly, it concerns the meet synthetic mordenites as cracking catalysts for virgin and various processed naphthas to yield more valuable products such as gas for use as fuel or chemicals plus a naphtha having an improved octane number.

Mordenite is a highly siliceous zeolite occurring in a number of localities, e.g., Nova Scotia (Case dOr), Iceland (Berufiord) and Idaho (Challis). This zeolite has been synthesized repeatedly and its molecular-sieve properties have been investigated in some detail. See in this connection R. M. Barrer, Die Trennung von Molekiilen mit Hilfe von Kristallsieben 35 Brennstoif-Chemie, 325334 (1954).

The mordenite type zeolite employed in the practice of the present invention is distinguished from the above known naturally occurring mordenite samples in that the mordenite employed in the present invention exhibits ability to adsorb cyclics, aromatics, naphthenes and isoparaflins and may be characterized as a mordenite having the ability to adsorb at least 1.5 wt. percent of benzene in the sodium form or 5.0 Wt. percent of benzene in the hydrogen form at a temperature of 205 F. and a pres-v sure of 0.5 atmosphere. These mordenite zeolites em: ployed in the practice of the present invention are chemically represented by the following formula:

0.9i0.2:Me ,,O:Al O :X SiO (anhydrous form) wherein Me is selected from the group consisting of metal cations and hydrogen-containing cations, n is the cation valence, and X is a number from about 9 to 15, and usually about 10. While this molar formula also represents naturally occurring mordenite, the naturally occurring variety thereof normally fails to show adsorptive affinity for cyclics and aromatics as indicated previously. Mordenite type zeolites employed in the practice of the present invention are commercially available from the Norton Company of Worcester, Massachusetts. These zeolites having an effective pore diameter in the range 'between about 6 to 10 A.

The mordenite zeolite is normally produced or found in its sodium form and must be treated to reduce its sodium content to less than wt. percent in order to serve as an effective cracking catalyst. This may be done by cation exchange with various salts of metals which have no detrimental effect on the cracking reaction, e.g., magne-.

sium, calcium, aluminum, the rare earths, or alternatively and preferably, by exchange with a hydrogen-containing cation, e.g., acid hydrogen or an ammonium ion containing the material. When employing the latter, the resulting ammonium derivative is then dried and calcined to decompose the ammonium ion to give what has been termed the hydrogen form of the zeolite.

The base exchange step with various metal cations or hydrogen-containing cations is normally conducted at temperatures of 50 to 150 F. by conventional base exchange with a suitable salt of the cation which is de- 3,247,098 Patented Apr. 19, 1966 sired to be introduced into the mordenite zeolite to replace sodium.

The conditions for the cracking reaction conducted in accordance with the present invention are generally those well known in the art. It involves cracking of a hydrocarbon stream, preferably petroleum naphthas boiling in the range of about 100 to 450 F. in the presence of the cracking catalyst of the present invention, i.e., an exchanged form of a mordenite zeolite having the ability to adsorb at least 1.5, preferably 5, wt. percent of benzene at 205 F. Reaction temperatures are generally from 700 to 1000 F., preferably 830 to 960 F. Feed rate of the reactant hydrocarbon stream can be from about 1.6 to 20.0 w./hr./w., preferably 5 to 10 w./hr./w. A diluent may be used in the cracking zone. Suitable diluents include steam and hydrogen gas introduced with the naphtha feed. When steam is used as a diluent, it may be employed in amounts of 1 to 20 wt. percent of the feed, preferably 2 to 10%. When operating without a diluent, or when employing steam as a diluent, the range of pressures employed is atmospheric to 25 p.s. i.g., preferably atmospheric to 15 p.s.i.g. -When hydrogen gas is used as a diluent, it may be introduced at a rate in the range of 1,000 to 10,000 cubic feet per barrel of feed, preferably 6,000 .to 8,000 cf./b. When employing hydroexamples.

sure in the range of 500l500 p.s.i.g., more preferably in the range of 800 to 1200 p.s.i.g.

Up to the present time there have been many attempts to crack light naphtha, i.e., naphthas boiling in the range of about to 450 F. Use of traditional cracking catalysts such as silica alumina, did not work as these catalysts were not sufiiciently active to cause any substantial upgrading of the naphtha stream. It has now unexpectedly been found that exchanged forms of a crystalline aluminosilicate zeolite, e. g., mordenite, are extremely active catalysts for the conversion of light naphtha to lighter components. The resultant light products are useful as fuel or chemicals while the resultant naphtha produced by the process has an improved octane number and therefore its commercial value is greatly enhanced. Conversions of up to 60% were obtained dependent on run length of 15 to 30 minutes. The results are made more surprising by 'the fact that a magnesium exchanged 13 A. sieve, such as for example the magnesium form of a synthetic faujasite sieve, gave very poor conversion, e.g., less than 10%, under similar conditions, in spite of the fact that such magnesium 13 A. aluminosilicates are known to be active cracking catalysts.

The various aspects and modifications of the present invention will be made more clearly apparent by reference to the following description and accompanying Example 1 A hydrogen form mordenite type zeolite, obtained from the Norton Company of Worcester, Massachusetts, and produced from a synthetic sodium form mordenite by treatment with dilute acid to replace the sodiumv ions with hydrogen ions was employed. It had a silica to alumina mole ratio of about 10 and a soda .content of about 0.9 wt. percent Na O and was capable ofadsorbing about 6.2 Wt. percent benzene, 5.0 wt. percentcyclohexane, or 4.6 wt. percent n-hexane at 205 F. and 0.5 atmosphere pressure. It had an effective pore size of about 6-10 A. This mordenite form was used as a cracking catalyst for converting light naphthas to lighter products of improved octane number. The results obtained using difierent feedstocks, feed rates, and temperatures are summarized in Table I.

TABLE I Feed #1, virgin Feed #2, Run No naphtha from 1 2 3 4 5 318/425 F. 6 7

South Louisiana catalytlc crude naphtha.

Temperature, F 950 950 950 900 950 950 Feed rate, w./hr./w 5. 8 1. 83 5. .5 5. 5 6. 3 2.0 Minutes fed 5 5 5 5 4 5 Product dish, wt. percent of feed:

H4- 0. 27 0. 89 0.10 0. 12 9. 07 0.14 0. 42 CH7 1. 3.74 0.71 0.58 0.29 0.53 1.53 cm. 0.91 1. 00 1.23 0.80 0.50 0.90 0.03 cm. 1.23 4.10 0.82 0.85 0. 41 0.00 1.90 can 2. 25 3.02 2. 73 1.75 1.32 2.20 0.85 cm. 9.50 22.02 7.30 11.09 5.80 3.81 9.70 cm. 1.07 2.25 2. 20 1. 00 0.88 1.57 0.58 i-omm 5.25 9.30 5.05 8.49 5.11 2.39 3.18 11.0.11. 2.12 4.48 1.07 2. 89 1.41 0.82 1. 40 0mm 0.83 1.03 1. 30 0.30 0.23 0. 41 0.18 i-CiHlz 1.01 2.74 1.01 2.71 1.18 0.59 0.92 11.031 0.25 0.45 0.22 0.33 0.10 0.21 0.17 cm. 0.15 0.49 0.03 0.10 0.04 0.10 0.24 04111 0.49 0.00 0.58 0.12 0.00 0.14 0.09 cm" 1.00 1.53 0.59 0.58 0.27 1.15 0.00 01+ 0.17 0. 30 0. 07 0. 00 0. 02 0. 0. 09

Total 28. 8 59. 4 20. 4 32. 5 10. 8 15. 0 22. 0 Liquid 05. 7 23. 5 09. 5 01. 0 80. 1 79. 8 04. 0 Carbon 5. 5 17. 1 4.1 5. 9 3.1 4. 0 13.4

Liquid prod., MS ana1., wt. percent:

1 Benzene 0. 11 0. 64 1. 07 0. 71 0. 87 0. 43 0. 18 1. 30 2. 97 Toluene 1. 47 3. 21 7. 01 3. 44 4. 57 2. 21 0. 79 4. 53 10. 87 G1 arom. 0. 09 8. 03 13.00 8. 74 11. 39 7. 84 3. 7. 84 15.20 C0 arom 2. 09 4 21 5. 50 3.93 5. 84 4. 43 19.80 22.01 23.03 01 arom 0.85 1 00 1. 00 1.02 1.44 1.30 10.19 10.01 12.99 011+ arom 0. 03 4. 24 2. 02 Naphthalenes 0. 1. 01 1. 0. 90 1. 13 1. 00 0. 57 3. 02 0. 31 Ind'mes 9. 96 6. 51 2. 58

Total arom 12.42 18 70 25. 24 17.21 57. 34 00.12 70.04 1. 70 3. 27 4. 29 2. 08 4. 93 1. 84 1. 79 20.04 21 57 10.14 23.22 12.20 10.08 0.74 3. 04 3. 14 2. 57 3. 91 0. 37 3. 77 2. 00 55. 59 53. 20 51. 70 52. 98 19. 09 17.59 13. 43

l A 20 cc. mierocatalytic cracking unit was used for these tests.

TABLE I continued TABLE I-O0r1t1nucd Run No A Feed iL/C 8 9 Run No 5322 7 8 9 ramco 5 a virgin naphtha vlrgm naphtha Te1nper8ture,F 950 950 .3 33 8 Feed rate, \v./hr./\v 1. 6 5. 2 3 343M? 0 1 MilllltGS led 5 5 2:3 D1\IP:: I Product distribution, wt. 55512 3 Percent feed 1 3 oMoP+3 EP" 0' 2 0' 1 0.41 0. 21 0 61+- 1'4 8'5 240 55 OBHB. I I' 2:3 010 .1: 3g Parallins- 84. 7 72. 2 O2 22 Naphthenes 12. 2 2. 0 33.40 10.10 0.19 22g 3% Examination of Table I reveals that the hydrogen ex- 2.17 change form of mordenite is an active catalytic agent for 1- 3g 333 light naphthas boiling in the range of about 100450 F. 0.35 0.18 Feed naphtha #1 of Table I, from South Louisiana crude, 2: was converted into a liquid product having a substantial- 0.27 0.10 ly lower boiling point. A relatively high concentration of 6380 4030 desirable aromatics was produced. Furthermore, the 25.7 54.7 cracking process yielded significant quantities of iso- Liquid product, wt percent. paraflins which increase the octane value of the product. p. 0. 2 Carbon-make was at a relatively low level especially in the 11%- cases where the feed rate was maintained between about 1% 5.5 to 5.8 w./hr./w. Greater arom'atization, as well 38 3: f5" 3 increased light parafiin production and carbon-make were 3,; P M EW evidenced when the feed rate was maintained at about 1 0 1&1 fg 1.8 W./hr./w. In the latter case the advantage of higher $205M? 3&3 conversion to aromatic and isoparaffinic products is ac- 11056 51 j "jg if com anied b reater carbon and as make. Lowerin 2,4 or 0 2 a of the reaction temperature from 950 F.-to 900 F. had the effect of increasing the quantity of aromatic and isoparatfinic products. i i i Use of the 318/ 425 F. catalytic naphtha feedstock resulted in a relative diminishing of the activity of .the catalyst. However, the mordenite catalyst did efi'ect a substantial lowering of the boiling point of the liquid product compared to the feed-stream. Also total aromatics concentration was increased (especially in the .case of a 2.0 w./hr./w. feed rate), as was the isoparaflin concentration. As in the case of the virgin naphtha #1 feedstock, carbon make changed inversely proportionally with the feed rate.

The mordenite catalyst of this example was also-shown to be active for the cracking of a C /C naphtha, identified as naphtha feed #B in Table I. Products from the cracking of this feed stream also show higher isoparaflinic and aromatic concentrations. As previously indicated, the faujasite type zeolite is relatively ineffective for the purposes of the present invention. By way of illustration, a .magnesium-faujasite catalyst, known to be a highly effective cracking catalyst, when used for the cracking of the above C /C naphtha (#3) at 10.00 F. and 1.3 v./v./hr., a diluent (steam) rate of 3300 s.c.f./-b. and a total time on feed of 30 minutes, converted only 8.9% of the feed to C; products.

Example 2 The effect of pressure on the cracking process was examined in a fixed-bed catalytic cracking unit having a capacity of 200 cc. of catalyst using the hydrogen form of mordenite described in Example 1. Results of these runs are summarized in Table II.

TABLE II.-NAPI-I'II-IA CONVERSION SCREENING STUDIES Feed, naphtha #1 1 Feed, catalytic 2 naphtha #2 Run N0 Boiling range, F 235/325 Operating conditions:

Temperature, F Pressure, p.s.i.g Feed rate, w./l1r./w. Minutes ted Diluent Diluent rate, c.f./b Product distribution,

wt. percent:

Carbon Ca-gas Ci+ in gas Liquid product Liquid product: Gravvity, API

MS type anal., Wt. percent:

Benzene Toluene. C8 arorn... C1] arom. Cm arorn 011+ arom Total atom Cyclopentanes Cyclohexancs Cond. naph 3. 64 Paratlins Gas distribution, wt.

percent:

Cracking activity is shown for both the 235/ 325 F. boiling range virgin naphtha and the 318/425 F. catalytic naphtha feeds under pressurized conditions. quantities of aromatics and isoparafiins produced were slightly lower than in the corresponding unpressurized 75 While the H runs, this was compensated for by the reduction in carbon make.

Example 3 Cracking tests were carried out in .a small laboratory scale fixed-bed unit with the hydrogen form of mordenite described. in Example 1. A summary of the effects of cycle time and space velocity is shown in Table III for the cracking of an N-decane feed stream. i

TABLE III.FIXED-BED CONVERSION OF N-DECANE A 832 F. AND ATMOSPHERIC PRESSURE 7 Cycle time, min 3 W./hr./w 1.4 1. 5 3. 8 10. 6 10.2

Conversion, wt. percent 49. 6 100. 0 55. 6 38. 9 59. 0 Product distribution, wt.

percent:

' Carbon 4. 2 12. 3 5.0 1. 9 5.0

.the high feed rate (10.2 w./hr./w.) resulted in 59% conversion but with more than twice as much 6.; gas as C -C fraction.

Example 4 A comparison of the hydrogen form of mordenite as described in Example 1 and a conventional cracking catalyst silica25% alumina) was run in a small laboratory scale fixed-bed unit on an N-decane feed stream. The results are summarized in Table IV.

TABLE IV.-FIXED-BED CONVERSION OF N-DECANE AT 832 F. AND ,ATMOSIHERIC PRESSURE; lO-l2-MINUTE CYCLE .IIME

Catalyst Mordenite- 75% silica-25% hydrogen form ,7 alumina W./hr./w- 3.8 3.9 Conversion, wt. percent 55. 6 11.4 Carbon 5.0 0.3 vC4-Gras 32. 1 7. 4 C5-C9. 18. 5 3.7

These tests show that the hydrogen form of mordenite is unexpectedly much 'more active for cracking decane than is a conventional silica-alumina cracking catalyst.

Example 5 A series of tests were run in a small laboratory scale fixed-bed unit employing mordenite exchanged with various cations to determine their activity as catalysts in the conversion of a cetane feed stream. Summarized data are shown in Table V.

TABLE V.CEIANE CRACKING WITH EXCI-IANGED MOR- DENITE CATALYSTS AT 832 F. AND ATMOSPHERIC PRESSURE; 20-MINUTE CYCLE TIME; 3.9-4.2 W./HR./W.

, Mordenite Form u Ca Mg Al I Co 11 Na Ni Conversion, wt. percent in 2 43.0 62.4 34.0 52.9 6.0 28.6 Product dist., wt. percent:

Carbon 4.3 1.7 2.8 2.2 2.4 1.1 2.6 C -Gas 17.3 18.2 26.3 11.7 26.4 0.1 15.3 0 -0 5 24.6 23.1 33.3 20.1 24.1 4.8 10.7

Of these various forms of mordenite catalysts, the most active is the one exchange with aluminum. Additionally the aluminum form has the decided advantage of the most favorable selectivity to liquid products at a reasonable carbon level. Another favorable material is the mordenite catalyst exchanged with magnesium which gave high conversion at relatively low carbon and gas make levels.

Example 6 The crystalline zeolite catalysts of the present invention are improved in form for the purposes of hydrocar- 8 jected to steam treatment at these temperature levels, e.g., to 30 hours at 850 to 1200 F. The spray dried composite of the crystalline zeolite embedded in the matrix material will generally contain about 5 to 40 wt. percent zeolite.

5 o bon conversion processes by admixing the crystalline f g i W 3 5" Bai i fi 5 2 1 zeolite with a siliceous cogel, preferably a silica-alumina f; iz t :2 cogel. The resulting composite, after drying, consists of ,E: compo e 1 us il a i; g crystalline zeolite distributed through a silica-metal oxide estzwere 9 e a cap We 6 T cogel matrix and is found to exhibit improved catalytic 1O alytlc crac mg at atmsP i Pressure" It can e Selectivity, stability and fiuidization properties seen that the compos1te catalyst 15 much more act1ve In order to incorporate the crystalline zeolite catalyst than commerclal slllca'alumlna ly Also the into the siliceous cogel matrix, the zeolite crystals, which cofnposlte Catalyst, 551366121113 the p y dried catalyst C011- may be in ither the odium for or in o e of th io ta1n1ng wt. percent of hydrogen-form mordenlte, at exchanged forms described previously, are added to a a given conversion g1ves less coke and a more unsatuhydrogel, such as a silica-alumina hydrogel and the rerated gas than either the pure s1l1ca-alurn1na or the pure sulting mixture is homogenized by passage through a hydrogen-form mordenite.

TABLE VI Catalyst SiOg/AlzOg H-Mordenite 2 33% H-Mordenite, 67% 10% H-Mordenite,

SiOz/AlgOa 3 90% SiOz/AlzO; 4

Temperature, F 950 900 900 950 950 900 900 950 950 950 Feed rate, w./hr./w 1. 8 5. 5 13.0 5. 5 1.83 4. 0 1. 8 1. 8 7. 86 2. 62 Cracking time, minutes 5 5 4 5 5 5 5 5 5 5 0. 04 0. 12 0. 07 0. 16 0.89 0. 07 0. 13 0. 39 0. 04 0. 0s 0. 53 0. 58 0.29 0. 71 3. 74 o. 44 0. 8G 2. 02 0. 23 0. 59 1.00 0.80 0.50 1. 23 1. G6 0. e7 0. 94 1. e0 0. 47 0.76 0. 0.85 0. 41 0.32 4. 1e 0. 5e 1. 11 2. 14 0. 17 0. 4c 4. 03 1. 75 1. 32 2. 73 3. 02 1.88 2. 30 3.82 2. 15 3. 47 2. 32 11. 69 5. 86 7. 3e 22. e2 6. 95 11. 80 15.71 1. 31 3.62

1. 79 1. 0e 0. 88 2. 26 2. 25 1. 02 1. 35 2. 52 1. 30 2. 39 3. 29 8.49 5. 11 5. 05 9. 3e 5. e1 10. 40 9. 94 1. 99 5. 40 0. 59 2. 89 1. 41 1. e7 4. 4s 1. 97 3. 0s 3. 4s 0. 1. 28

5. e7 12. 44 7. 40 8.98 16. 09 9. 14. 83 15. 94 3.80 9. 13 83. 81 65. 87 81. 05 73. 91 30. 72 76. 63 60. 63 49. 18 91. 23 79. 96 Carbon 2.3 5.9 3.1 4.1 17.1 3.2 7.4 9.2 0.6 1.9

1 Commercial fluid Sim/A1 0 cracking catalyst produced by Davison Chemical Corp. 2 Hydrogen-form mordenite powder pilled and the pills crushed to fluidizable size. a Hydrogen-form mordenite and Slog/A1303 powders mixed, pilled, and the pills cracked to fluidizable size. 4 Hydrogen-form mordenite powder added to Slo /A1 0; hydrogel and spray dried to fluidizable size. blending apparatus, such as a colloid mill, ball mill, Example 7 and the like. The homogenized slurry is then formed into particles of a size range desired for fluidized bed operations. This is conveniently accomplished by spray drying, although other methods may be employed. The matrix particles are then preferably water washed to remove water-soluble material and oven dried. The dry product may then be subjected to a calcination treatment at temperatures above about 500 F., e.g., 500 to 1500 F., for about 8 to 24 hours. It may also be sub- TABLE VII Catalyst Slog/A1203 l II-Mordenite 2 10% II-Mordenite, 3

% SlOr/AlzOs Temperature, F 950 950 950 950 950 Feed rate, w./hr./ 1. 6 5. 2 1. 6 2. 33 2. 33 Cracking time, minutes 5 5 5 5 3 Products, wt percent of feed:

Hz. 0. 01 0. 21 0. 41 0.05 0. 05 0. l6 0. 2. 40 0. 38 0. 49 0. 32 1. 26 1.29 O. 72 0. 94 0.13 1. 29 3. 29 O. 40 (l. 55 1. 27 3. 42 2.02 3. 05 3. 66 0. 61 16. 10 33. 40 4. 67 6. 57

0. 06 0.00 0. 19 0. 58 0. 68 0.15 3. 38 5. 64 1.70 2.15 11-C4Hm O. 10 2. 86 4. 28 0. 82 1. 30

Total 04 0. 31 6. 24 10. 11 3.10 4.13

Total 0 liquid 96.19 65. 53 36.58 86. 39 81. 56 Carbon 1.0 5.0 10.5 1. 2 2.0

1 Commercial fluid Slog/A1103 cracking catalyst produced by 2 Hydrogen-form mordenite powder pilled and the Davison Chemical Corp. ills crushed to fluidizable size.

Samples of the Ca, Mg, A1, C0, H and Ni forms of mordenite incorporated into a silica-alumina matrix as described above are utilized in the cracking process described in Example 1. They are found to exhibit superior catalytic properties.

Various modifications may be made to the present invention. For example, the present cracking process may utilize many of the techniques normally found in conventional cracking processes. Such changes may be made by one skilled in the art without departing from the spirit of the present invention as defined by the claims.

What is claimed is:

1. An improved process for cracking light naphtha streams to obtain improved product quality which comprises subjecting said light naphthas boiling in the range of about 100 to 450 F. to cracking conditions in the presence of a mordenite catalyst, said catalyst comprising a mordenite zeolite having a silica to alumina mol ratio of about 9 to 15, an effective pore diameter in the range of about 6 to A., and having the ability to adsorb at least 1.5 wt. percent of benzene at 205 F. at 0.5 atmosphere, said zeolite being further characterized in that it contains less than 5 wt. percent Na O, and recovering products boiling below said light naphthas and a naphtha product having improved octane number.

2. The process of claim 1 wherein said mordenite catalyst had been base exchanged with a cation selected from the group consisting of hydrogen-containing cations, calcium ion, magnesium ion, aluminum ion, cobalt ion and nickel ion.

3. The process of claim 2 wherein said mordenite catalyst had been base exchanged with a hydrogen-contain ing cation.

4. The process of claim 1 wherein said mordenite catalyst had been base exchanged with aluminum.

5. The process of claim 1 wherein said mordenite catalyst had been base exchanged with magnesium.

6. The process of claim 1 wherein said mordenite catalyst is embedded in a silica-metal oxide cogel matrix.

7. The process of claim 6 wherein said metal oxide is aluminum oxide.

8. The process of claim 6 wherein said mordenite catalyst had been base exchanged with a cation selected from the group consisting of hydrogen-containing cations, calcium ion, magnesium ion, aluminum ion, cobalt ion and nickel ion.

9. A process for upgrading petroleum naphtha boiling in the range of about to 450 F. which comprises contacting said naphtha with a mordenite catalyst at a temperature of 700 to 1000 F. and a pressure of 0 to 25 p.s.i.g. to thereby convert said naphtha to lower boiling products having improved octane number, said mordenite catalyst being of the synthetic variety, containing less than 5 wt. percent Na O, and having a silica to alumina mole ratio of about 9 to 15 and an effective pore diameter in the range of about 6 to 10 A., and being further characterized by the ability to adsorb at least 1.5 wt. percent benzene at 205 F. and 0.5 atmosphere.

10. The process of claim 9 wherein said mordenite catalyst had been base exchanged with a cation selected from the group consisting of hydrogen-containing cations, calcium ion, magnesium ion, aluminum ion, cobalt ion and nickel ion.

11. A process for upgrading petroleum naphtha boiling in the range of about 100 to 450 P. which comprises contacting said naphtha with an aluminum-containing mordenite catalyst at a temperature of 700 to 1000 F. and a pressure of 0 to 25 p.s.i.g. to thereby convert said naphtha to lower boiling products having improved octane number, said aluminum-containing mordenite catalyst being of the synthetic variety and having a silica to alumina mole ratio of about 9 to 15 and an effective pore diameter of about 6 to 10 A., and being further characterized by the ability to adsorb at least 1.5 wt. percent benzene at 205 F. and 0.5 atmosphere, said mordenite having been base exchanged with an aluminum ion to reduce its Na 0 content to less than 5 wt. percent.

References Cited by the Examiner UNITED STATES PATENTS 2,962,435 11/1960 Fleck et a1. 208- 3,039,953 6/1962 Eng 208120 3,114,696 12/1963 Weisz 208-66 3,140,251 7/1964 Plank et a1. 2081'20 3,190,939 6/1965 Benesi 260-683.65

DELBERT E. GANTZ, Primary Examiner.

ALPHONSO D. SULLIVAN, PAUL M. COUGHLAN,

Examiners. 

1. AN IMPROVED PROCESS FOR CRACKING LIGHT NAPHTHA STREAMS TO OBTAIN IMPROVED PRODUCT QUALITY WHICH COMPRISES SUBJECTING SAID LIGHT NAPHTHAS BOILING IN THE RANGE OF ABOUT 100* TO 450*F. TO CRACKING CONDITIONS IN THE PRESENCE OF A MORDENITE CATALYST, SAID CATALYST COMPRISING A MORDENITE ZEOLITE HAVING A SILICA TO ALUMINA MOL RATIO OF ABOUT 9 TO 15, AN EFFECTIVE PORE DIAMETER IN THE RANGE OF ABOUT 6 TO 10 A., AND HAVING THE ABILITY TO ADSORB AT LEAST 1.5 WT. PERCENT OF BENZENE AT 205*F. AT 0.5 ATMOSPHERE, SAID ZEOLITE BEING FURTHER CHARACTERIZED IN THAT IT CONTAINS LESS THAN 5 WT. PERCENT NA2O, AND RECOVERING PRODUCTS BOILING BELOW SAID LIGHT NAPHTHAS AND A NAPHTHA PRODUCT HAVING IMPROVED OCTANE NUMBER. 